Enhanced catalyst performance for production of vinyl terminated propylene and ethylene/propylene macromers

ABSTRACT

This invention relates to a transition metal catalyst compound represented by the structure: 
                         
wherein
     M is hafnium or zirconium;
       each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;   
       each R 1  and R 3  are, independently, a C 1  to C 8  alkyl group; and   each R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14  are, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three of the R 10 -R 14  groups are not hydrogen, compositions thereof and methods of use thereof to prepare polymers.

PRIORITY

This application is a divisional of U.S. Ser. No. 13/072,279, filed Mar.25, 2011.

STATEMENT OF RELATED APPLICATIONS

This application is related to U.S. Ser. No. 12/143,663, filed on Jun.20, 2008 (Published as WO 2009/155471); U.S. Ser. No. 12/487,739, filedon Jun. 19, 2009 (Published as WO 2009/155472); U.S. Ser. No.12/488,066, filed on Jun. 19, 2009 (Published as WO 2009/155510);12/488,093 filed on Jun. 19, 2009 (Published as WO 2009/155517); andU.S. Ser. No. 12/642,453, filed Dec. 18, 2009; which is acontinuation-in-part application of U.S. Ser. No. 12/533,465 filed onJul. 31, 2009, which claims priority to and the benefit of U.S. Ser. No.61/136,172, filed on Aug. 15, 2008; which are all incorporated byreference herein.

This invention also relates to the following concurrently filedapplications:

a) U.S. Ser. No. 13/072,280, filed Mar. 25, 2011, entitled “NovelCatalysts and Methods of Use Thereof to Produce Vinyl TerminatedPolymers”;

b) U.S. Ser. No. 13/072,189, filed Mar. 25, 2011, entitled “AmineFunctionalized Polyolefin and Methods for Preparation Thereof”;

c) U.S. Ser. No. 13/072,383, filed Mar. 25, 2011, entitled “DiblockCopolymers Prepared by Cross Metathesis”;

d) U.S. Ser. No. 13/072,261, filed Mar. 25, 2011, entitled “AmphiphilicBlock Polymers Prepared by Alkene Metathesis”;

e) U.S. Ser. No. 13/072,288, filed Mar. 25, 2011, entitled “VinylTerminated Higher Olefin Polymers and Methods to Produce Thereof”;

f) U.S. Ser. No. 13/072,305, filed Mar. 25, 2011, entitled“Hydrosilylation of Vinyl Macromers with Metallocenes”;

g) U.S. Ser. No. 13/072,432, filed Mar. 25, 2011, entitled “OlefinTriblock Polymers via Ring-Opening Metathesis Polymerization”;

h) U.S. Ser. No. 13/072,330, filed Mar. 25, 2011, entitled “BlockCopolymers from Silylated Vinyl Terminated Macromers”;

i) U.S. Ser. No. 13/072,249, filed Mar. 25, 2011, entitled “VinylTerminated Higher Olefin Copolymers and Methods to Produce Thereof”; and

j) U.S. Ser. No. 61/467,681, filed Mar. 25, 2011, entitled “BranchedVinyl Terminated Polymers and Methods for Production Thereof”.

FIELD OF THE INVENTION

This invention relates to catalyst compounds useful for olefinpolymerization particularly propylene-ethylene oligomerization toproduce vinyl terminated oligomers.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing about 6 to about 20 carbonatoms, have been used as intermediates in the manufacture of detergentsor other types of commercial products. Such alpha-olefins have also beenused as monomers, especially in linear low density polyethylene.Commercially produced alpha-olefins are typically made by oligomerizingethylene. Longer chain alpha-olefins, such as vinyl-terminatedpolyethylenes are also known and can be useful as building blocksfollowing functionalization or as macromonomers.

Allyl terminated low molecular weight solids and liquids of ethylene orpropylene have also been produced, typically for use as branches inpolymerization reactions. See, for example, Rulhoff, Sascha andKaminsky, (“Synthesis and Characterization of Defined BranchedPoly(propylene)s with Different Microstructures by Copolymerization ofPropylene and Linear Ethylene Oligomers (C _(n)=26-28) withMetallocenes/MAO Catalysts,” Macromolecules 16 2006, pp. 1450-1460), andKaneyoshi, Hiromu et al. (“Synthesis of Block and Graft Copolymers withLinear Polyethylene Segments by Combination of Degenerative TransferCoordination Polymerization and Atom Transfer Radical Polymerization,”Macromolecules 38 2005, pp. 5425-5435).

Further, U.S. Pat. No. 4,814,540 discloses bis(pentamethylcyclopentadienyl) hafnium dichloride, bis(pentamethyl cyclopentadienyl)zirconium dichloride and bis(tetramethyl n-butyl cyclopentadienyl)hafnium dichloride with methylalumoxane in toluene or hexane with orwithout hydrogen to make allylic vinyl terminated propylenehomo-oligomers having a low degree of polymerization of 2-10. Theseoligomers do not have high Mn's and have at least 93% allylic vinylunsaturation. Likewise, these oligomers lack comonomer and are producedat low productivities with a large excess of alumoxane (molar ratio ≧600Al/M; M=Zr, Hf). Additionally, no less than 60 wt % solvent(solvent+propylene basis) is present in all of the examples.

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-87) used[Cp*₂MMe(THT)]+[BPh₄], M=Zr and Hf) to make propylene oligomers. ForM=Zr a broad product distribution with oligomers up to C₂₄ (Mn 336) wasobtained at room temperature. Whereas for M=Hf only the dimer4-methyl-1-pentene and the trimer 4,6-dimethyl-1-heptene were formed.The dominant termination mechanism appeared to be beta-methyl transferfrom the growing chain back to the metal center, as was demonstrated bydeuterium labeling studies.

X. Yang et al. (Angew. Chem., Intl Edn., Engl., 31, 1992, pp. 1375-1377)disclose amorphous, low molecular weight polypropylene made at lowtemperatures where the reactions showed low activity and product having90% allylic vinyls, relative to all unsaturations, by ¹H NMR.Thereafter, Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp.1025-1032), disclose the use of bis(pentamethylcyclopentadienyl)zirconium and bis(pentamethylcyclopentadienyl)hafnium centers topolymerize propylene and obtained beta-methyl termination resulting inoligomers and low molecular weight polymers with “mainly allyl- andiso-butyl-terminated” chains. As is the case in U.S. Pat. No. 4,814,540,the oligomers produced do not have at least 93% allyl chain ends, an Mnof about 500 to about 20,000 g/mol (as measured by ¹H NMR), and thecatalyst has low productivity (1-12,620 g/mmol metallocene.hr; >3000wppm Al in products).

Similarly, Small and Brookhart (Macromol., 32, 1999, pp. 2120-2130)discloses the use of a pyridylbis amido iron catalyst in a lowtemperature polymerization to produce low molecular weight amorphouspropylene materials apparently having predominant or exclusive 2,1 chaingrowth, chain termination via beta-hydride elimination, and high amountsof vinyl end groups.

Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107) disclosesmaterials with up to about 81 percent vinyl termination made usingdimethylsilyl bis(2-methyl, 4-phenyl-indenyl) zirconium dichloride andmethylalumoxane in toluene at about 120° C. The materials have a Mn ofabout 12,300 (measured with ¹H NMR) and a melting point of about 143° C.

Macromolecules, 33, 2000, pp. 8541-8548 discloses preparation ofbranch-block ethylene-butene polymer made by reincorporation of vinylterminated polyethylene, said branch-block polymer made by a combinationof Cp₂ZrCL₂ and (C₅Me₄SiMe₂NC₁₂H₂₃)TiCl₂ activated with methylalumoxane.

Moscardi et al. (Organomet., 20, 2001, pp. 1918) disclose the use ofrac-dimethylsilylmethylene bis(3-t-butyl indenyl) zirconium dichloridewith methylalumoxane in batch polymerizations of propylene to producematerials where “ . . . allyl end group always prevails over any otherend groups, at any [propene].” In these reactions, morphology controlwas limited and approximately 60% of the chain ends are allylic.

Coates et al. (Macromol., 2005, 38, pp. 6259-6268) disclose preparationof low molecular weight syndiotactic polypropylene ([rrrr]=0.46-0.93)with about 100% allyl end groups using bis(phenoxyimine)titaniumdichloride ((PHI)₂TiCl₂) activated with modified methyl alumoxane (Al/Timolar ratio=200) in batch polymerizations run between −20 and +20° C.for four hours. For these polymerizations, propylene was dissolved intoluene to create a 1.65 M toluene solution. Catalyst productivity wasvery low (0.95 to 1.14 g/mmol Ti/hr).

JP 2005-336092 A2 discloses the manufacture of vinyl-terminatedpropylene polymers using materials such as H₂SO₄ treatedmontmorillonite, triethylaluminum, triisopropyl aluminum, where theliquid propylene is fed into a catalyst slurry in toluene. This processproduces substantially isotactic macromonomers not having a significantamount of amorphous material.

Rose et al (Macromolecules 2008, 41, pp. 559-567) disclosepoly(ethylene-co-propylene) macromonomers not having significant amountsof iso-butyl chain ends. Those were made with bis(phenoxyimine) titaniumdichloride activated with modified methylalumoxane (Al/Ti molar ratiorange 150 to 292) in semi-batch polymerizations (30 psi propylene addedto toluene at 0° C. for 30 min, followed by ethylene gas flow at 32 psiof over-pressure at about 0° C. for polymerization times of 2.3 to 4hours to produce E-P copolymer having an Mn of about 4800 to 23,300. Infour reported copolymerizations, allylic chain ends decreased withincreasing ethylene incorporation roughly according to the equation:% allylic chain ends(of total unsaturations)=−0.95(mol % ethyleneincorporated)+100.

For example, 65% allyl (compared to total unsaturation) was reported forE-P copolymer containing 29 mol % ethylene. This is the highest allylpopulation achieved. For 64 mol % incorporated ethylene, only 42% of theunsaturations are allylic. Productivity of these polymerizations rangedfrom 0.78×10² g/mmol Ti/hr to 4.62×10² g/mmol Ti/hr.

Prior to this work, Zhu et al. reported only low (−38%) vinyl terminatedethylene-propylene copolymer made with the constrained geometrymetallocene catalyst [C₅Me₄(SiMe₂N-tert-butyl)TiMe₂ activated withB(C₆F₅)₃ and MMAO (Macromol., 2002, 35, pp. 10062-10070 and Macromol.Rap. Commun., 2003, 24, pp. 311-315).

Janiak and Blank summarize a variety of work related to oligomerizationof olefins (Macromol. Symp., 236, 2006, pp. 14-22).

Rodriguez et al. in U.S. Patent No. 2005/0159299 disclose polymerizationand oligomerization with catalyst compounds on a specifically treatedsupport and exemplifies polymerization with a catalyst compound ofdimethylsilyl bis(2-methyl, 4-phenyl indenyl) zirconium dimethyl on acapped support. Such catalysts however typically produce about 50% vinyland about 50% vinylidene terminal unsaturations (of the termini that areunsaturated).

Example 18 of WO 95/27717 discloses using a dimethylsilanediylbis(octahydrofluorenyl) zirconium dichloride compound withmethylalumoxane at 50° C. to make homo-propylene oligomer reported tohave 95% allyl-termination, an “oligomerization degree” of 45 (whichlikely equates to an Mn of about 1890), and an estimated Al content of90,000 ppm. The activities also appear low.

In all the prior art, no catalysts are shown to produce high allylicchain unsaturations in high yields, a wide range of molecular weight,and with high productivity for propylene-based polymerizations,especially propylene-ethylene copolymerizations. Thus, there is still aneed for propylene based macromonomers that have allyl terminationpresent in high amounts (90% or more), with control over a wide range ofmolecular weights that can be made at commercial temperatures (e.g., 25°C. and above) and commercial rates (5,000 g/mmol/hr productivity ormore). Alternately, there is a need for propylene ethylene oligomershaving structural robustness (where addition of ethylene raisesviscosity and the solubility parameter—relative to propylene—andprovides for potential crystallizable ethylene runs, while loweringglass transition temperature). Further, there is a need for propylenebased reactive materials having vinyl termination which can befunctionalized (and/or derivatized) and used in additive applications.Further there is a need for new, active catalysts that can operate atcommercial conditions to produce such.

SUMMARY OF THE INVENTION

Hafnium (Hf) and zirconium (Zr) catalyst compounds containingbenzindenyl based ligands are provided. The catalyst compounds areuseful, with or without activators, to polymerize olefins, particularlyα-olefins, or other unsaturated monomers, particularlypropylene-ethylene oligomerization to produce vinyl terminatedoligomers. Systems and processes to oligomerize and/or polymerize one ormore unsaturated monomers using the catalyst compound, as well as theoligomers and/or polymers produced therefrom are also provided.

The catalyst compounds can be represented by the following structures:

wherein:

-   M is hafnium or zirconium, preferably hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may be the same or    different as R³ and preferably are both methyl; and-   each R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted hydrocarbyl or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three of R¹⁰-R¹⁴ groups are not hydrogen (alternately four    of R¹⁰-R¹⁴ groups are not hydrogen, alternately five of R¹⁰-R¹⁴    groups are not hydrogen).

Preferably all five groups of R¹⁰-R¹⁴ are methyl, or four of the R¹⁰-R¹⁴groups are not hydrogen and at least one of the R¹⁰-R¹⁴ group is a C₂ toC₈ substituted hydrocarbyl or unsubstituted hydrocarbyl (preferably atleast two, three, four or five of R¹⁰-R¹⁴ groups are a C₂ to C₈substituted or unsubstituted hydrocarbyl).

In one embodiment, R¹ and R³ are methyl groups, R² is a hydrogen, R⁴-R⁹are all hydrogen, R¹⁰-R¹⁴ are all methyl groups and each X is a methylgroup.

This invention further relates to a process to produce vinyl terminatedmacromonomers, e.g., polymers having at least 30% allyl chain ends, andpreferably an Mn of from 100 g/mol or more, preferably 200 g/mol to100,000 g/mol, preferably 200 to 60,000 g/mol using the catalystsdescribed herein.

This invention further relates to processes to make such polymers,including homogeneous processes. This invention also relates to ahomogeneous process, preferably a bulk process, to make such polymers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of productivity versus propylene concentration.

FIG. 2 is molecular weight versus propylene concentration.

DEFINITIONS

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, and an arrow indicates that the bond maybe dative.

As used herein, the new notation for the Periodic Table Groups is usedas described in Chemical and Engineering News, 63(5), 27 (1985).

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom or a heteroatom containing group.For example methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group and ethyl alcohol is an ethyl group substituted with an —OHgroup.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁ to C₂₀ radicals, that may be linear, branched, orcyclic (aromatic or non-aromatic); and include substituted hydrocarbylradicals as defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with a heteroatom or heteroatomcontaining group, preferably with at least one functional group, such ashalogen (Cl, Br, I, F), NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least oneheteroatom has been inserted within the hydrocarbyl radical, such ashalogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂,GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently, hydrogenor a hydrocarbyl.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this disclosure, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl, and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, including, but not limited to ethylene, propylene, and butene,the olefin present in such polymer or copolymer is the polymerized formof the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt % to 55 wt %, it is understood that the merunit in the copolymer is derived from ethylene in the polymerizationreaction and said derived units are present at 35 wt % to 55 wt %, basedupon the weight of the copolymer. A “polymer” has two or more of thesame or different mer units. A “homopolymer” is a polymer having merunits that are the same. A “copolymer” is a polymer having two or moremer units that are different from each other. A “terpolymer” is apolymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An oligomer is a polymer having a lowmolecular weight. In some embodiments, an oligomer has an Mn of 21,000g/mol or less (preferably 2,500 g/mol or less) in other embodiments, anoligomer has a low number of mer units (such as 75 mer units or less).

For the purposes of this disclosure, the term “α-olefin” includesethylene. Non-limiting examples of α-olefins include ethylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene,1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene,1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst” and “catalyst compound” are defined to mean acompound capable of initiating catalysis. In the description herein, thecatalyst may be described as a catalyst precursor, a pre-catalystcompound, or a transition metal compound, and these terms are usedinterchangeably. A catalyst compound may be used by itself to initiatecatalysis or may be used in combination with an activator to initiatecatalysis. When the catalyst compound is combined with an activator toinitiate catalysis, the catalyst compound is often referred to as apre-catalyst or catalyst precursor. A “catalyst system” is combinationof at least one catalyst compound, at least one activator, an optionalco-activator, and an optional support material, where the system canpolymerize monomers to polymer. For the purposes of this invention andthe claims thereto, when catalyst systems are described as comprisingneutral stable forms of the components, it is well understood by one ofordinary skill in the art, that the ionic form of the component is theform that reacts with the monomers to produce polymers.

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments a co-activator can be pre-mixed with the catalystcompound to form an alkylated catalyst compound, also referred to as analkylated invention compound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight (measured by ¹HNMR unless stated otherwise, Mw is weight average molecular weight(measured by Gel Permeation Chromatography), and Mz is z averagemolecular weight (measured by Gel Permeation Chromatography), wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD) is defined to be Mw divided by Mn. Unless otherwise noted, allmolecular weight units (e.g., Mw, Mn, Mz) are g/mol.

“Allyl chain ends” (also referred to as “allylic vinyl groups” or“allylic vinyl end groups”) is defined to be a polymer having at leastone terminus represented by (CH₂CH—CH₂-polymer), formula I:

where the “••••” represents the polymer chain. In a preferredembodiment, the allyl chain ends is represented by the formula II:

The amount of allyl chain ends is determined using ¹H NMR at 120° C.using deuterated tetrachloroethane as the solvent on a 500 MHz machineand in selected cases confirmed by ¹³C NMR. Resconi has reported protonand carbon assignments (neat perdeuterated tetrachloroethane used forproton spectra while a 50:50 mixture of normal and perdeuteratedtetrachloroethane was used for carbon spectra; all spectra were recordedat 100° C. on a Bruker AM 300 spectrometer operating at 300 MHz forproton and 75.43 MHz for carbon) for vinyl terminated propyleneoligomers in J American Chemical Soc., 114, 1992, pp. 1025-1032 that areuseful herein.

“Isobutyl chain end” also referred to as “isobutyl end group” is definedto be a polymer having at least one terminus represented by the formula:

where M represents the polymer chain. In a preferred embodiment, theisobutyl chain end is represented by one of the following formulae:

where M represents the polymer chain.

The percentage of isobutyl end groups is determined using ¹³C NMR (asdescribed below) and the chemical shift assignments in Resconi et al, J.Am. Chem. Soc., 1992, 114, pp. 1025-1032 for 100% propylene polymers andas set forth in FIG. 2 of WO 2009/155471 for E-P copolymers.

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallyl chain ends.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiarybutyl, p-tBu is para-tertiary butyl, nBu is normal butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is triisobutyln-octylaluminum, MAO is methylalumoxane, pMe is para-methyl, Ar* is2,6-diisopropylaryl, Bz is benzyl, THF is tetrahydrofuran, RT is roomtemperature and tol is toluene.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the use of the catalysts described herein toproduce a vinyl terminated polymer (VTM), which is a polymer having atleast 30% (preferably at least 40%, preferably at least 50%, preferablyat least 60%, preferably at least 70%, preferably at least 80%,preferably at least 90%, preferably at least 95%) allyl chain ends, andpreferably an Mn of 2000 g/mol or more, preferably 200 to 60,000 g/mol,preferably 200 to 100,000 g/mol.

This invention also relates to the use of the catalysts described hereinto produce a propylene polymer, comprising propylene and less than 0.5wt % comonomer, preferably 0 wt % comonomer, wherein the polymer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR (preferably 500 to 15,000,        preferably 700 to 10,000, preferably 800 to 8,000 g/mol,        preferably 900 to 7,000, preferably 1000 to 6,000, preferably        1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0;    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

This invention also relates to a propylene copolymer produced with thecatalysts described herein as having an Mn of 300 to 30,000 g/mol asmeasured by ¹H NMR (preferably 400 to 20,000, preferably 500 to 15,000,preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol %propylene (preferably 15 to 85 mol %, preferably 20 to 80 mol %,preferably 30 to 75 mol %, preferably 50 to 90 mol %) and 10 to 90 mol %(preferably 85 to 15 mol %, preferably 20 to 80 mol %, preferably 25 to70 mol %, preferably 10 to 50 mol %) of one or more alpha-olefincomonomers (preferably ethylene, butene, hexene, or octene, preferablyethylene), wherein the polymer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100{alternately 1.20 (−0.94 (mol % ethyleneincorporated)+100), alternately 1.50 (−0.94 (mol % ethyleneincorporated)+100)}), when 10 to 60 mol % ethylene is present in thecopolymer; 2) X=45 (alternately 50, alternately 60), when greater than60 and less than 70 mol % ethylene is present in the copolymer; and 3)X=(1.83*(mol % ethylene incorporated) −83, {alternately 1.20 [1.83*(mol% ethylene incorporated) −83], alternately 1.50 [1.83*(mol % ethyleneincorporated) −83]}), when 70 to 90 mol % ethylene is present in thecopolymer. Alternately X is 80% or more, preferably 85% or more,preferably 90% or more, preferably 95% or more.

In an alternate embodiment, the polymer has at least 80% isobutyl chainends (based upon the sum of isobutyl and n-propyl saturated chain ends),preferably at least 85% isobutyl chain ends, preferably at least 90%isobutyl chain ends. Alternately, the polymer has an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.35:1.0, preferably 0.9:1 to1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

This invention also relates to a propylene polymer prepared with thecatalysts described herein, comprising more than 90 mol % propylene(preferably 95 to 99 mol %, preferably 98 to 9 mol %) and less than 10mol % ethylene (preferably 1 to 4 mol %, preferably 1 to 2 mol %),wherein the polymer has:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR (preferably 500 to 20,000, preferably 600to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000,preferably 900 to 8,000, preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;and

less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferablyless than 1000 ppm, preferably less than 500 ppm, preferably less than100 ppm).

This invention also relates to a propylene polymer prepared with thecatalysts described herein, comprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

an Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR(preferably 200 to 15,000, preferably 250 to 15,000, preferably 300 to10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

This invention also further relates to a propylene polymer preparedusing the catalysts described herein, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, preferably butene), wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR (preferably 200 to 12,000, preferably 250to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

This invention also further relates to a propylene polymer produced withthe catalysts described herein, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20,000g/mol, as measured by ¹H NMR (preferably 200 to 15,000, preferably 250to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

This invention relates to the use of the catalysts described herein toproduce a propylene copolymer having an Mn of 100 to 60,000 g/mol (asmeasured by ¹H NMR) comprising 10 to 90 mol % propylene and 10 to 90 mol% of ethylene, wherein the copolymer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in thecopolymer, and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the copolymer, and 3) X=(1.83*(mol % ethyleneincorporated) −83), when 70 to 90 mol % ethylene is present in thecopolymer.

This invention further relates to the use of the catalysts describedherein to produce a propylene polymer, comprising more than 90 mol %propylene and less than 10 mol % ethylene, wherein the polymer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum.

This invention further relates to the use of the catalysts describedherein to produce a propylene polymer, comprising at least 50 mol %propylene and from 10 to 50 mol % ethylene, wherein the polymer has: atleast 90% allyl chain ends, Mn of about 150 to about 10,000 g/mol (asmeasured by ¹H NMR), and an isobutyl chain end to allylic vinyl groupratio of 0.8:1 to 1.3:1.0, wherein monomers having four or more carbonatoms are present at from 0 to 3 mol %.

This invention further relates to the use of the catalysts describedherein to produce a propylene polymer, comprising at least 50 mol %propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % C₄ toC₁₂ olefin, wherein the polymer has: at least 87% allyl chain ends(alternately at least 90%), an Mn of about 150 to about 10,000 g/mol,(as measured by ¹H NMR), and an isobutyl chain end to allylic vinylgroup ratio of 0.8:1 to 1.35:1.0.

This invention further relates to the use of the catalysts describedherein to produce a propylene polymer, comprising at least 50 mol %propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % diene,wherein the polymer has: at least 90% allyl chain ends, an Mn of about150 to about 10,000 g/mol (as measured by ¹H NMR), and an isobutyl chainend to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

This invention further relates to the use of the catalysts describedherein to produce a propylene homopolymer, wherein the polymer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum.

For purpose of this invention and the claims thereto, the term vinylterminated polymer (also referred to as vinyl terminated polyolefin)includes vinyl terminated polymers and vinyl terminated copolymers.Preferred vinyl terminated polyolefins produced herein include vinylterminated isotactic polypropylene (preferably having a melting point of100° C. or more, preferably 150° C. or more), and vinyl terminatedpolyethylene (preferably having a melting point of 100° C. or more,preferably 115° C. or more).

In a preferred embodiment, any vinyl terminated polyolefin describedherein has at least 75% allyl chain ends (relative to totalunsaturations), preferably at least 80%, preferably at least 85%,preferably at least 90%, preferably at least 95%.

In a preferred embodiment, any vinyl terminated polyolefin describedherein has an Mn of 200 g/mol or more, alternately from 200 to 60,000g/mol, preferably from 200 to 50,000 g/mol, preferably from 200 to40,000 g/mol, preferably from 500 to 30,000 g/mol, preferably from 1000to 10,000 g/mol.

In a preferred embodiment, the vinyl terminated polyolefin producedherein comprises at least 10 mol % (alternately at least 20 mol %,alternately at least 40 mol %, alternately at least 60 mol %) of a C₄ orgreater olefin (such as butene, pentene, octene, nonene, decene,undecene, dodecene, preferably C₅ to C₄₀ alpha olefin such as pentene,octene, nonene, decene, undecene, dodecene) and has: 1) at least 30%allyl chain ends (relative to total unsaturations), preferably at least40%, preferably at least 50%, preferably at least 60%, preferably atleast 70%, preferably at least 75%, preferably at least 80%, preferablyat least 85%, preferably at least 90%, preferably at least 95%; and 2)an Mn of from 200 to 60,000 g/mol, preferably from 200 to 50,000 g/mol,preferably from 500 to 40,000 g/mol.

In a preferred embodiment, the vinyl terminated polyolefin producedherein is a homopolymer or copolymer comprising one or more C2 to C40olefins, preferably C2 to C40 alpha olefins, preferably ethylene,propylene, butene, pentene, hexene, octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, and/or 4-methylpentene-1. In a preferredembodiment, the vinyl terminated polyolefin produced herein has an Mn offrom 200 to 60,000 g/mol, preferably from 500 to 30,000 g/mol,preferably from 1,000 to 20,000 g/mol and is a homopolymer or copolymercomprising two or more C₂ to C₄₀ olefins, preferably two or more or C₃to C₂₀ alpha olefins, preferably two or more of ethylene, propylene,butene, pentene, hexene, octene, nonene, decene, undecene, and/ordodecene and has at least 30% allyl chain ends (relative to totalunsaturations), preferably at least 40%, preferably at least 50%,preferably at least 60%, preferably at least 70%, preferably at least75%, preferably at least 80%, preferably at least 85%, preferably atleast 90%, preferably at least 95%.

In a preferred embodiment, the vinyl terminated polyolefin producedherein is a polymer having an Mn of from 200 to 21,000 g/mol (preferably500 to 15,000, preferably 800 to 20,000 g/mol) comprising one or morealpha olefins selected from the group consisting of C₂ to C₄₀ alphaolefins, preferably ethylene, propylene, butene, pentene, hexene,octene, nonene, decene, undecene, and dodecene. In a preferredembodiment, the vinyl terminated polyolefin produced herein is a polymerhaving an Mn of from 500 to 21,000 g/mol (preferably 700 to 21,000,preferably 800 to 20,000 g/mol) comprising two or more alpha olefinsselected from the group consisting of C₂ to C₄₀ alpha olefins,preferably C₃ to C₂₀ alpha olefins, preferably two or more alpha olefinsselected from the group consisting ethylene, propylene, butene, pentene,hexene, octene, nonene, decene, undecene, and dodecene and has at least30% allyl chain ends (relative to total unsaturations), preferably atleast 40%, preferably at least 50%, preferably at least 60%, preferablyat least 70%, preferably at least 75%, preferably at least 80%,preferably at least 85%, preferably at least 90%, preferably at least95%.

Preferably the vinyl terminated polyolefin produced herein is anethylene polymer, e.g., a homo-polymer of ethylene or copolymer ofethylene and up to 50 mol % (preferably from 0.5 to 25 mol %, preferablyfrom 1 to 20 mol %) of one or more C₃ to C₄₀ alpha olefin comonomers,preferably selected from the group consisting of propylene, butene,pentene, hexene, octene, nonene, decene, undecene, and dodecene.Alternately, the vinyl terminated polyolefin produced herein is apropylene polymer, e.g., a homopolymer of propylene or copolymer ofpropylene and up to 50 mol % (preferably from 0.5 to 25 mol %,preferably from 1 to 20 mol %) of one or more C₂ and C₄ to C₄₀ alphaolefin comonomers, preferably selected from the group consisting ofethylene, butene, pentene, hexene, octene, nonene, decene, undecene, anddodecene. Alternately, the vinyl terminated polyolefin produced hereinis a copolymer of ethylene and/or propylene and a C₄ to C₄₀alpha-olefin, such as butene, pentene, hexene, octene, nonene, decene,undecene, and dodecene and has at least 30% allyl chain ends (relativeto total unsaturations), preferably at least 40%, preferably at least50%, preferably at least 60%, preferably at least 70%, preferably atleast 75%, preferably at least 80%, preferably at least 85%, preferablyat least 90%, preferably at least 95%. Alternately, the vinyl terminatedpolyolefin produced herein is a copolymer of ethylene and/or propyleneand two or more C₄ to C₄₀ alphaolefins, such as butene, pentene, hexene,octene, nonene, decene, undecene, and dodecene. In a particularlypreferred embodiment, the vinyl terminated polyolefin produced hereinhas at least 30% allyl chain ends, relative to total unsaturations(preferably at least 40%, preferably at least 50%, preferably at least60%, preferably at least 70%, preferably at least 75%, preferably atleast 80%, preferably at least 85%, preferably at least 90%, preferablyat least 95%) and the vinyl terminated polyolefin produced herein is acopolymer of:

-   1) ethylene and two or more C₄ to C₄₀ alpha olefins, such as butene,    pentene, hexene, octene, nonene, decene, undecene, dodecene; or-   2) propylene and two or more C₄ to C₄₀ alpha olefins, such as    butene, pentene, hexene, octene, nonene, decene, undecene, dodecene;    or-   3) ethylene and propylene and two or more C₄ to C₄₀ alphaolefins,    such as butene, pentene, hexene, octene, nonene, decene, undecene,    dodecene; or-   4) propylene and two or more alpha olefins selected from butene,    pentene, hexene, octene, nonene, decene, undecene, and dodecene.

In a preferred embodiment, the vinyl terminated polyolefin producedherein is a polymer having an Mn of greater than 1,000 g/mol (preferablyfrom 2,000 to 60,000, preferably 5,000 to 50,000 g/mol) comprising oneor more alpha olefins selected from the group consisting of C₂ to C₄₀alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,octene, nonene, decene, undecene, dodecene, and 4-methyl-pentene-1.Preferably, the vinyl terminated polyolefin produced herein is anethylene polymer, e.g., a homopolymer of ethylene or copolymer ofethylene and up to 50 mol % (preferably from 0.5 to 25 mol %, preferablyfrom 1 to 20 mol %) of one or more C₃ to C₄₀ alpha olefin comonomers,preferably selected from the group consisting of propylene, butene,pentene, hexene, octene, nonene, decene, undecene, dodecene, and4-methyl-pentene-1. Alternately, the vinyl terminated polyolefinproduced herein is propylene polymer, e.g., a homopolymer of propyleneor a copolymer of propylene and up to 50 mol % (preferably from 0.5 to25 mol %, preferably from 1 to 20 mol %) of one or more C₂ to C₄₀ alphaolefins comonomers, preferably selected from the group consisting ofethylene, butene, pentene, hexene, octene, nonene, decene, undecene,dodecene, and 4-methyl-pentene-1 having at least 30% allyl chain ends,relative to total unsaturations (preferably at least 40%, preferably atleast 50%, preferably at least 60%, preferably at least 70%, preferablyat least 75%, preferably at least 80%, preferably at least 85%,preferably at least 90%, preferably at least 95%).

In another embodiment, the vinyl terminated polyolefin produced hereinmay be one or more vinyl terminated polyolefins having an Mn (measuredby ¹H NMR) of 200 g/mol or more, (preferably 300 to 60,000 g/mol, 400 to50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000g/mol); and comprising: (i) from about 20 to 99.9 mol % (preferably fromabout 25 to about 90 mol %, from about 30 to about 85 mol %, from about35 to about 80 mol %, from about 40 to about 75 mol %, or from about 50to about 95 mol %) of at least one C₅ to C₄₀ olefin (preferably C₅ toC₃₀ α-olefins, more preferably C₅-C₂₀ α-olefins, preferably, C₅-C₁₂α-olefins, preferably pentene, hexene, heptene, octene, nonene, decene,undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene,cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substitutedderivatives thereof, and isomers thereof, preferably hexane, heptene,octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene,1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene,cyclopentene, norbornene, and their respective homologs and derivatives,preferably norbornene); and (ii) from about 0.1 mol % to about 80 mol %of propylene (preferably from about 5 mol % to about 70 mol %, fromabout 10 mol % to about 65 mol %, from about 15 mol % to about 55 mol %,from about 25 mol % to about 50 mol %, or from about 30 mol % to about80 mol %); wherein the vinyl terminated polyolefins produced herein hasat least 40% allyl chain ends, relative to total unsaturations(preferably at least 50%, at least 60%, at least 70%, at least 80%, atleast 90%, at least 95%); and, optionally, an isobutyl chain end toallylic chain end ratio of less than 0.70:1 (preferably less than0.65:1, less than 0.60:1, less than 0.50:1, or less than 0.25:1), andfurther optionally, an allyl chain end to vinylidene chain end (asdetermined by ¹H NMR) ratio of more than 2:1 (preferably more than2.5:1, more than 3:1, more than 5:1, or more than 10:1), and furtheroptionally, an allyl chain end to vinylene chain end ratio of greaterthan 10:1 (preferably greater than 15:1, or greater than 20:1); and evenfurther optionally preferably substantially no isobutyl chain ends(preferably less than 0.1 wt % isobutyl chain ends).

In another embodiment, the vinyl terminated polyolefins produced hereinmay be one or more vinyl terminated polyolefins having an Mn (measuredby ¹H NMR) of 200 g/mol or more (preferably 300 to 60,000 g/mol, 400 to50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000g/mol) and comprises: (i) from about 80 to 99.9 mol % (preferably 85 to99.9 mol %, more preferably 90 to 99.9 mol %) of at least one C₄ olefin(preferably 1-butene); and (ii) from about 0.1 to 20 mol % of propylene,preferably 0.1 to 15 mol %, more preferably 0.1 to 10 mol %; wherein thevinyl terminated polymer has at least 40% allyl chain ends, relative tototal unsaturations, preferably at least 50%, at least 60%, at least70%; or at least 80%; and, optionally, an isobutyl chain end to allylicchain end ratio of less than 0.70:1, less than 0.65:1, less than 0.60:1,less than 0.50:1, or less than 0.25:1, and further optionally, an allylchain end to vinylidene chain end ratio of more than 2:1, more than2.5:1, more than 3:1, more than 5:1, or more than 10:1; and, furtheroptionally, an allyl chain end to vinylene chain end ratio of greaterthan 10:1 (preferably greater than 15:1, or greater than 20:1); and,even further optionally, preferably substantially no isobutyl chain ends(preferably less than 0.1 wt %).

In a preferred embodiment, the vinyl terminated polymer produced hereincomprises at least 10 mol % (alternately at least 20 mol %, alternatelyat least 40 mol %, alternately at least 60 mol %) of a C₄ or greaterolefin (such as butene, pentene, octene, nonene, decene, undecene,dodecene) and has: 1) at least 30% allyl chain ends (relative to totalunsaturation), preferably at least 40%, preferably at least 50%,preferably at least 60%, preferably at 70%, preferably at least 75%,preferably at least 80%, preferably at least 85%, preferably at least90%, preferably at least 95%; and 2) an Mn of from 200 to 60,000 g/mol,preferably from 200 to 50,000 g/mol, preferably from 500 to 40,000g/mol.

In another embodiment, the vinyl terminated polyolefin produced here inmay be one or more vinyl terminated polyolefin having an Mn (measured by¹H NMR) of 200 g/mol or more (preferably 300 to 60,000/gmol, preferably400 to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to10,000 g/mol); and comprising: (i) from about 20 mol % to about 99.9 mol% (preferably from about 25 mol % to about 90 mol %, preferably fromabout 30 mol % to about 85 mol %, preferably from about 35 mol % toabout 80 mol %, preferably from about 40 mol % to about 75 mol %, orfrom about 50 mol % to about 95 mol %) of at least one C₅ to C₄₀α-olefins (preferably C₅ to C₃₀ α-olefins, preferably C₅ to C₂₀α-olefins, preferably C₅-C₁₂ α-olefins, preferably pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene, norbornene,norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,7-oxanorbornadiene, substituted derivatives thereof, and isomersthereof, preferably hexane, heptene, octene, nonene, decene, dodecene,cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbornadiene, and their respectivehomologs and derivatives, preferably norbornene, norbornadiene, anddicyclopentadiene); and (ii) from about 0.1 mol % to 80 mol % ofpropylene (preferably from about 5 mol % to 70 mol %, preferably fromabout 10 mol % to about 65 mol %, preferably from about 15 mol % toabout 55 mol %, preferably from about 25 mol % to about 50 mol %,preferably from about 30 mol % to about 80 mol %); wherein the vinylterminated polyolefin has at least 40% allyl chain ends (preferably atleast 50%, at least 60%, at least 70%, at least 80%, at least 90%, atleast 95%); and, optionally, an isobutyl chain end to allylic chain endratio of less than 0.70:1 (preferably less than 0.65:1, less than0.60:1, less than 0.50:1, less than 0.25:1); and, further optionally, anallyl chain end to vinylidene chain end (as determined by ¹H NMR) ratioof more than 2:1 (preferably more than 2.5:1, more than 3:1, more than5:1, more than 10:1); and, further optionally, an allyl chain end tovinylene chain end ratio of great than 10:1 (preferably greater than15:1, greater than 20:1); and, even further optionally, preferablysubstantially no isobutyl chain ends (preferably less than 0.1 wt %).

In particular embodiments herein, the invention relates to a compositioncomprising vinyl terminated polymers produced herein having an Mn of atleast 200 g/mol, (preferably 200 to 100,000 g/mol, preferably 200 to75,000 g/mol, preferably 200 to 60,000 g/mol, preferably 300 to 60,000g/mol, or preferably 750 to 30,000 g/mol) (measured by ¹H NMR)comprising of one or more (preferably two or more, three or more, fouror more, and the like) C₄ to C₄₀ (preferably C₅ to C₃₀, C₆ to C₂₀, or C₈to Cl₂, preferably butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof) higher olefinderived units, where the vinyl terminated higher olefin polymercomprises substantially no propylene derived units (preferably less than0.1 wt % propylene); and wherein the higher olefin polymer has at least5% (at least 10%, at least 15%, at least 20%, at least 30%, at least40%, at least 50%, at least 60%, at least 70%; at least 80%, at least90%, or at least 95%) allyl chain ends, relative to total unsaturations;and optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 2:1 (preferably greater than 2.5:1, greater than 3:1,greater than 5:1, or greater than 10:1); and, further optionally, anallyl chain end to vinylene chain end ratio of greater than 10:1(preferably greater than 15:1, or greater than 20:1); and, even furtheroptionally, preferably substantially no isobutyl chain ends (preferablyless than 0.1 wt % isobutyl chain ends). In some embodiments, thesehigher olefin vinyl terminated polyolefins may comprise ethylene derivedunits, preferably at least 5 mol % ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol % ethylene, preferably at least35 mol % ethylene, preferably at least 45 mol % ethylene, preferably atleast 60 mol % ethylene, preferably at least 75 mol % ethylene, orpreferably at least 90 mol % ethylene).

Any of the polymers prepared herein preferably have less than 1400 ppmaluminum, preferably less than 1000 ppm aluminum, preferably less than500 ppm aluminum, preferably less than 100 ppm aluminum, preferably lessthan 50 ppm aluminum, preferably less than 20 ppm aluminum, preferablyless than 5 ppm aluminum.

Vinyl terminated polyolefins produced herein may be isotactic, highlyisotactic, syndiotactic, or highly syndiotactic propylene polymer,particularly isotactic polypropylene. As used herein, “isotactic” isdefined as having at least 10% isotactic pentads, preferably having atleast 40% isotactic pentads of methyl groups derived from propyleneaccording to analysis by ¹³C-NMR. As used herein, “highly isotactic” isdefined as having at least 60% isotactic pentads according to analysisby ¹³C-NMR. In a desirable embodiment, VTM (preferably polypropylene)has at least 85% isotacticity. As used herein, “syndiotactic” is definedas having at least 10% syndiotactic pentads, preferably at least 40%,according to analysis by ¹³C-NMR. As used herein, “highly syndiotactic”is defined as having at least 60% syndiotactic pentads according toanalysis by ¹³C-NMR. In another embodiment, the VTM (preferablypolypropylene) has at least 85% syndiotacticity.

In a preferred embodiment, the propylene polymer comprises less than 3wt % of functional groups selected from hydroxide, aryls and substitutedaryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen,nitrogen, and carboxyl, preferably less than 2 wt %, more preferablyless than 1 wt %, more preferably less than 0.5 wt %, more preferablyless than 0.1 wt %, more preferably 0 wt %, based upon the weight of thepolymer.

Any polymer produced using the catalyst described herein may have anM_(n) of 150 to 60,000 g/mol, 200 to 50,000 g/mol, preferably 250 to30,000 g/mol, preferably 300 to 20,000 g/mol, preferably 400 to 5,000g/mol, preferably 750 to 2,000 g/mol. Further a desirable molecularweight range can be any combination of any upper molecular weight limitwith any lower molecular weight limit described above. M_(n) isdetermined according to the methods described below in the examplessection.

Any polymer produced using the catalyst described herein may have aglass transition temperature (Tg) of less than 0° C. or less (asdetermined by differential scanning calorimetry as described below),preferably −10° C. or less, more preferably −20° C. or less, morepreferably −30° C. or less, more preferably −50° C. or less.

In some embodiments, the polymer produced by the catalyst describedherein preferably contains less than 80 wt % of C₄ olefin(s), (such asisobutylene n-butene, 2-butene, isobutylene, and butadiene), based uponthe weight of the oligomer, preferably less than 10 wt %, preferably 5wt %, preferably less than 4 wt %, preferably less than 3 wt %,preferably less than 2 wt %, preferably less than 1 wt %, preferablyless than 0.5 wt %, preferably less than 0.25 wt % of C₄ olefin(s) basedupon the weight of the polymer.

Alternately, the polymer may contain less than 20 wt % of C₄ or moreolefin(s), (such as C₄ to C₃₀ olefins, typically such as C₄ to C₁₂olefins, typically such as C₄, C₆, C₈, C₁₂, olefins, etc.), based uponthe weight of the polymer, preferably less than 10 wt %, preferably 5 wt%, preferably less than 4 wt %, preferably less than 3 wt %, preferablyless than 2 wt %, preferably less than 1 wt %, preferably less than 0.5wt %, preferably less than 0.25 wt % of C₄ olefin(s) based upon theweight of the polymer, as determined by ¹³C NMR

In another embodiment, the polymer composition produced herein comprisesat least 50 wt % (preferably at least 75 wt %, preferably at least 90 wt%, based upon the weight of the polymer composition) olefins having atleast 36 carbon atoms (preferably at least 51 carbon atoms, preferablyat least 102 carbon atoms) as measured by ¹H NMR assuming oneunsaturation per chain.

In another embodiment, the polymer composition produced herein comprisesless than 20 wt % dimer and trimer (preferably less than 10 wt %,preferably less than 5 wt %, more preferably less than 2 wt %, basedupon the weight of the polymer composition), as measured by GasChromatography. Products are analyzed by gas chromatography (Agilent6890N with auto-injector) using helium as a carrier gas at 38 cm/sec. Acolumn having a length of 60 m (J & W Scientific DB-1, 60 m×0.25 mmI.D.×1.0 μm film thickness) packed with a flame ionization detector(FID), an Injector temperature of 250° C., and a Detector temperature of250° C. are used. The sample was injected into the column in an oven at70° C., then heated to 275° C. over 22 minutes (ramp rate 10° C./min to100° C., 30° C./min to 275° C., hold). An internal standard, usually themonomer, is used to derive the amount of dimer or trimer product that isobtained. Yields of dimer and trimer product are calculated from thedata recorded on the spectrometer. The amount of dimer or trimer productis calculated from the area under the relevant peak on the GC trace,relative to the internal standard.

In another embodiment, the polymer produced herein contains less than 25ppm hafnium, preferably less than 10 ppm hafnium, preferably less than 5ppm hafnium based on the yield of polymer produced and the mass ofcatalyst employed.

In another embodiment, the polymers described herein may have a meltingpoint (DSC first melt) of from 60 to 130° C., alternately 50 to 100° C.In another embodiment, the polymers described herein have no detectablemelting point by DSC following storage at ambient temperature (23° C.)for at least 48 hours.

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

In another embodiment, the vinyl terminated polymer produced herein hasa branching index, g′_(vis), of 0.98 or less, alternately 0.96 or less,alternately 0.95 or less, alternately 0.93 or less, alternately 0.90 orless, alternately 0.85 or less, alternately 0.80 or less, alternately0.75 or less, alternately 0.70 or less, alternately 0.65 or less,alternately 0.60 or less, alternately 0.55 or less.

In another embodiment, the polymers produced herein are a liquid at 25°C.

In another embodiment, the polymers produced herein have an Mw of 1,000to about 200,000 g/mol, alternately 2000 to 150,000 g/mol, alternately3,000 to 30,000 g/mol and/or an Mz of about 1700 to about 150,000 g/mol,alternately 800 to 100,000 g/mol.

In another embodiment, any of the vinyl terminated polyolefins describedor useful herein have 3-alkyl vinyl end groups (where the alkyl is a C₁to C₃₈ alkyl), also referred to as a “3-alkyl chain ends” or a “3-alkylvinyl termination”, represented by the formula:

3-alkyl vinyl end group

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, preferably a C₁ to C₂₀ alkyl group, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,docecyl, and the like. The amount of 3-alkyl chain ends is determinedusing ¹³C NMR as set out below.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl chain ends(preferably at least 10%, at least 20%, at least 30%, at least 40%, atleast 50%, at least 60%, at least 70%, at least 80%, at least 90%, atleast 95%), relative to total unsaturation.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% of 3-alkyl+allyl chain ends,(e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably atleast 10% 3-alkyl+allyl chain ends, at least 20% 3-alkyl+allyl chainends, at least 30% 3-alkyl+allyl chain ends; at least 40% 3-alkyl+allylchain ends, at least 50% 3-alkyl+allyl chain ends, at least 60%3-alkyl+allyl chain ends, at least 70% 3-alkyl+allyl chain ends; atleast 80%3-alkyl+allyl chain ends, at least 90% 3-alkyl+allyl chainends; at least 95% 3-alkyl+allyl chain ends, relative to totalunsaturation.

In some embodiments, the oligomers of this invention have an Mw/Mn (byGPC-DRI) of 1.5 to 20, alternately 1.7 to 10.

Mw, Mn, and Mz are measured by Gel Permeation Chromatography using aHigh Temperature Size Exclusion Chromatograph (either from WatersCorporation or Polymer Laboratories), equipped with a differentialrefractive index detector (DRI), a light scattering LS detector and aviscometer. Experimental details are described in: T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,pp. 6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B LS columns are used. The nominal flow rate is 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 45° C. Solvent for theSEC experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the sizeexclusion chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 135° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector are purged. Flow rate in the apparatusis then increased to 0.5 ml/minute, and the DRI is allowed to stabilizefor 8 to 9 hours before injecting the first sample. The concentration,c, at each point in the chromatogram is calculated from thebaseline-subtracted DRI signal, I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mol, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, Light Scattering from Polymer Solutions, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2\; A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], P(θ) is the form factor for a monodisperse randomcoil, and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}( {{{dn}/d}\; c} )}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and =690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(S) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\Sigma\;{c_{i}\lbrack\eta\rbrack}_{i}}{\Sigma\; c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

¹³C NMR data was collected at 120° C. in a 10 mm probe using a Varianspectrometer with a ¹Hydrogen frequency of at least 400 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ at concentrations between10 wt % to 15 wt % prior to being inserted into the spectrometer magnet.Prior to data analysis spectra were referenced by setting the chemicalshift of the (—CH₂—)_(n) signal where n>6 to 29.9 ppm. Chain ends forquantization were identified using the signals shown in the table below.N-butyl and n-propyl were not reported due to their low abundance (lessthan 5%) relative to the chain ends shown in the table below.

Chain End ¹³CNMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm

Polypropylene microstructure is determined by ¹³C-NMR spectroscopy,including the concentration of isotactic and syndiotactic diads ([m] and[r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Thedesignation “m” or “r” describes the stereochemistry of pairs ofcontiguous propylene groups, “m” referring to meso and “r” to racemic.Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 100 MHz (or higher) NMR spectrometer.Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculationsinvolved in the characterization of polymers by NMR are described by F.A. Bovey in Polymer Conformation and Configuration (Academic Press, NewYork 1969) and J. Randall in Polymer Sequence Determination, ¹³C-NMRMethod (Academic Press, New York, 1977).

¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45°, 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons.

The ¹H NMR chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene 4.70-4.84 2 Vinylene 5.31-5.55 2 Trisubstituted5.11-5.30 1

ICPES (Inductively Coupled Plasma Emission Spectrometry), which isdescribed in J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644, is used to determine the amount of anelement in a material.

Polymerization Process

This invention also relates to a process, preferably a homogeneous orbulk process, to make the vinyl terminated polymers described herein. Ina preferred embodiment, monomers (such as propylene) and optionalcomonomers (such as ethylene) can be polymerized by reacting a catalystsystem (comprising the catalysts described herein and optionally, one ormore activators) with the olefins. Other additives may also be used, asdesired, such as scavengers and/or hydrogen. Any conventionalsuspension, homogeneous, bulk, solution, slurry, or high-pressurepolymerization process can be used. Such processes can be run in abatch, semi-batch, or continuous mode. Homogeneous polymerizationprocesses are preferred. (A homogeneous polymerization process isdefined to be a process where at least 90 wt % of the product is solublein the reaction media.) A bulk homogeneous process is particularlypreferred. (A bulk process is defined to be a process where monomerconcentration in all feeds to the reactor is 70 volume % or more.)Alternately no solvent or diluent is present or added in the reactionmedium, (except for the small amounts used as the carrier for thecatalyst system or other additives, or amounts typically found with themonomer; e.g., propane in propylene).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopars); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, and 1-decene. Mixtures of the foregoing are also suitable. Ina preferred embodiment, aliphatic hydrocarbon solvents are preferred,such as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably less than0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration for the polymerizationis 60 volume % solvent or less, preferably 40 volume % or less,preferably 20 volume % or less. Preferably the polymerization is run ina bulk process.

Suitable additives to the polymerization process can include one or morescavengers, promoters, modifiers, chain transfer agents, reducingagents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

In a preferred embodiment hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

In an alternate embodiment, the activity of the catalyst is at least 50g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering the reaction zone,preferably 20% or more, preferably 30% or more, preferably 50% or more,preferably 80% or more. In an alternate embodiment, the productivity isat least 4500 g/mmol/hour, preferably 5000 or more g/mmol/hour,preferably 10,000 or more g/mmol/hr, preferably 50,000 or moreg/mmol/hr.

In an alternate embodiment, the productivity is at least 80,000g/mmol/hr, preferably at least 150,000 g/mmol/hr, preferably at least200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably atleast 300,000 g/mmol/hr. Preferred polymerizations can be run at typicaltemperatures and/or pressures, such as from 0° C. to 300° C., preferably25° C. to 150° C., preferably 40° C. to 120° C., preferably 45° C. to80° C., and preferably from atmospheric pressure to 10 MPa, preferably0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4MPa.

In a typical polymerization, the residence time of the reaction is up to60 minutes, preferably between 5 to 50 minutes, preferably between 10 to40 minutes.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated macromers. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the VTM'sthen, the alumoxane has been treated to remove free alkyl aluminumcompounds, particularly trimethyl aluminum.

Further, in a preferred embodiment, the activator used herein to producethe vinyl terminated macromer is a bulky activator as defined herein andis discrete.

In a preferred embodiment, little or no scavenger is used in the processto produce the vinyl terminated macromers. Preferably, scavenger (suchas tri alkyl aluminum) is present at zero mol %, alternately thescavenger is present at a molar ratio of scavenger metal to transitionmetal of less than 100:1, preferably less than 50:1, preferably lessthan 15:1, preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0° C. to 300° C. (preferably 25° C. to 150° C.,preferably 40° C. to 120° C., preferably 45° C. to 80° C.); and 2) isconducted at a pressure of atmospheric pressure to 10 MPa (preferably0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4MPa); and 3) is conducted in an aliphatic hydrocarbon solvent (such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof; preferably where aromatics arepresent in the solvent at less than 1 wt %, preferably at 0.5 wt %,preferably at 0 wt % based upon the weight of the solvents); and 4)wherein the catalyst system used in the polymerization comprises lessthan 0.5 mol %, preferably 0 mol % alumoxane, alternately the alumoxaneis present at a molar ratio of aluminum to transition metal less than500:1, preferably less than 300:1, preferably less than 100:1,preferably less than 1:1); and 5) the polymerization occurs in onereaction zone; and 6) the productivity of the catalyst compound is atleast 80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr,preferably at least 200,000 g/mmol/hr, preferably at least 250,000g/mmol/hr, preferably at least 300,000 g/mmol/hr); and 7) optionallyscavengers (such as trialkyl aluminum compounds) are absent (e.g.,present at zero mol %, alternately the scavenger is present at a molarratio of scavenger metal to transition metal of less than 100:1,preferably less than 50:1, preferably less than 15:1, preferably lessthan 10:1); and 8) optionally hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa)(preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa)). In a preferred embodiment, the catalystsystem used in the polymerization comprises no more than one catalystcompound. A “reaction zone” is a vessel where polymerization takesplace, for example a batch reactor. A polymerization occurring in twostages in two different reactors would have two reaction zones.

Catalyst Compound

Catalyst compounds useful herein include one or more compound(s)represented by the formula:

wherein

-   M is hafnium or zirconium, preferably hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may be the same or    different as R³ and preferably are both methyl; and-   each R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6    carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, provided, however, that at least three of    R¹⁰-R¹⁴ groups are not hydrogen (alternately four of R¹⁰-R¹⁴ groups    are not hydrogen, alternately five of R¹⁰-R¹⁴ groups are not    hydrogen).

In a preferred embodiment, all five groups of R¹⁰-R¹⁴ are methyl, orfour of the R¹⁰-R¹⁴ groups are not hydrogen and at least one of theR¹⁰-R¹⁴ group is a C₂ to C₈ substituted or unsubstituted hydrocarbyl(preferably at least two, three, four or five of R¹⁰-R¹⁴ groups are a C₂to C₈ substituted or unsubstituted hydrocarbyl).

In one embodiment, R¹ and R³ are methyl groups, R² is a hydrogen, R⁴-R⁹are all hydrogens, R¹⁰-R¹⁴ are all methyl groups and each X is a methylgroup.

Catalyst compounds that are particularly useful in this inventioninclude (CpMe₅)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂, (CpMe₅)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂,(CpMe₄n-propyl)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl) (1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl, 3-ethylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl, 3-ethylbenz[e]indenyl)HfMe₂, and the zirconiumanalogs thereof. In an alternate embodiment, the “dimethyl” (Me₂) afterthe transition metal in the list of catalyst Hf and Zr compounds aboveis replaced with a dihalide (such as dichloride or difluoride) or abisphenoxide, particularly for use with an alumoxane activator.

Activators and Activation Methods for Catalyst Compounds

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O-sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxide,or amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio. Alternatepreferred ranges include from 1:1 to 500:1, alternately 1:1 to 200:1,alternately 1:1 to 100:1, alternately from 1:1 to 50:1.

Aluminum alkyl or organoaluminum compounds which may be utilized asco-activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diethyl zinc, and the like.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459) or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators. Morepreferred activators are the ionic activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to20 carbon atoms (including substituted aryls). More preferably, thethree groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl,or mixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994, all of which are herein fullyincorporated by reference.

Ionic catalysts can be prepared by reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the catalyst compound forms ananion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions.

Preferred compounds useful as an activator component in the preparationof the ionic catalyst systems used in the process of this inventioncomprise a cation, which is preferably a Bronsted acid capable ofdonating a proton, and a compatible non-coordinating anion which anionis relatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, amines and the like. Two classes ofcompatible non-coordinating anions have been disclosed in EP 0 277 003 Aand EP 0 277 004 A1: 1) anionic coordination complexes comprising aplurality of lipophilic radicals covalently coordinated to and shieldinga central charge-bearing metal or metalloid core; and 2) anionscomprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators useful hereininclude a cation and an anion component, and may be represented by thefollowing formula:(L-H)_(d) ⁺(A ^(d−))  (14)wherein L is an neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d isan integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotonated

Lewis bases capable of protonating a moiety, such as an alkyl or aryl,from the bulky ligand metallocene containing transition metal catalystprecursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 2, 3, 4, 5, or 6;n−k=d; M is an element selected from Group 13 of the Periodic Table ofthe Elements, preferably boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms with the proviso that in not more than 1 occurrenceis Q a halide. Preferably, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, more preferably each Q is a fluorinatedaryl group, and most preferably each Q is a pentafluoryl aryl group.Examples of suitable A^(d−) also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts, such as di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts, such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Preferably, the activator is N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

In one embodiment, activation methods using ionizing ionic compounds notcontaining an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP 0 426 637 A1, EP 0 573 403 A1, andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base, such as an olefinic monomer. “Compatible”non-coordinating anions are those which are not degraded to neutralitywhen the initially formed complex decomposes. Further, the anion willnot transfer an anionic substituent or fragment to the cation so as tocause it to form a neutral four coordinate metallocene compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those that are compatible, stabilizethe catalyst cation in the sense of balancing its ionic charge at +1,yet retain sufficient lability to permit displacement by anethylenically or acetylenically unsaturated monomer duringpolymerization. Any metal or metalloid that can form a compatible,weakly coordinating complex may be used or contained in thenoncoordinating anion. Suitable metals include, but are not limited to,aluminum, gold, and platinum. Suitable metalloids include, but are notlimited to, boron, aluminum, phosphorus, and silicon. A stoichiometricactivator can be either neutral or ionic. The terms ionic activator, andstoichiometric ionic activator can be used interchangeably. Likewise,the terms neutral stoichiometric activator, and Lewis acid activator canbe used interchangeably. In addition to these activator compounds orco-catalysts, scavengers are used such as tri-isobutyl aluminum ortri-octyl aluminum.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP 0 427 697 A1 and EP 0 520 732A1 for illustrations of analogous Group-4 metallocene compounds. Also,see the methods and compounds of EP 0 495 375 A1. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX ^(e+))_(d)(A ^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; A is a non-coordinating anion having the charge d−; and dis 1, 2, or 3. Examples of cationic oxidizing agents include:ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺².Preferred embodiments of A^(d−) are those anions previously defined withrespect to the Bronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

The typical non-alumoxane activator-to-catalyst-precursor ratio is a 1:1molar ratio. Alternate preferred ranges include from 0.1:1 to 100:1,alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1alternately from 1:1 to 1000:1. A particularly useful range is from0.5:1 to 10:1, preferably 1:1 to 5:1.

Bulky Activators

The process of this invention can also use a “bulky activator.”

“Bulky activator” as used herein refers to anionic activatorsrepresented by the formula:

where:

-   each R₁ is, independently, a halide, preferably a fluoride;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl group or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl group (preferably R₂ is a fluoride or a    perfluorinated phenyl group);-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    group or a siloxy group of the formula —O—Si—R_(a), where R_(a) is a    C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a    fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); wherein    R₂ and R₃ can form one or more saturated or unsaturated, substituted    or unsubstituted rings (preferably R₂ and R₃ form a perfluorinated    phenyl ring);-   L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or    3; and-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the boron, B, atom    each have a molecular volume of greater than 250 cubic Å,    alternately greater than 300 cubic Å, or alternately greater than    500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962 to 964. Molecular volume (MV), in units of cubicÅ, is calculated using the formula: MV=8.3V_(s), where V_(s) is thescaled volume. V_(s) is the sum of the relative volumes of theconstituent atoms, and is calculated from the molecular formula of thesubstituent using the following table of relative volumes. For fusedrings, the V_(s) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron.

Molecular MV Formula of Per Total Structure of boron each subst. MVActivator substituents substituent V_(S) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],and the types disclosed in U.S. Pat. No. 7,297,653.

Useful activators useful with the above catalysts include:dimethylaniliniumtetrakis(pentafluorophenyl) borate,dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B].

Activator Combinations

It is within the scope of this invention that catalyst compounds can becombined with one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157; 5,453,410; European publication EP 0 573 120B1; PCT publications WO 94/07928 and WO 95/14044. These documents alldiscuss the use of an alumoxane in combination with an ionizingactivator.

Monomers

Useful olefins for polymerization herewith include polymers of C₂ to C₄₀olefins, preferably alpha-olefins, preferably ethylene and propylene.

The vinyl terminated polymers prepared herein are typically polymers ofethylene and/or propylene but can also be copolymers of ethylene and/orpropylene with comonomers of C₄ to C₄₀ olefins, preferably ethyleneand/or C₅ to C₂₅ olefins, or preferably C₆ to C₁₈ olefins. The C₄ to C₄₀olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups.Exemplary C₄ to C₄₀ olefin monomers include butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene, norbornene,norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,7-oxanorbornadiene, substituted derivatives thereof, and isomersthereof, preferably hexane, heptane, octene, nonene, decene, dodecene,cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbornadiene, and their respectivehomologs and derivatives, preferably norbornene, norbornadiene, anddicyclopentadiene, as shown below.

Preferred vinyl terminated polymers produced herein include,homopolypropylene, propylene copolymerized with ethylene, and propylenecopolymerized with ethylene and/or C₄ to C₄₀ olefins as listed above.

In a preferred embodiment, the polymer comprises 0.1 mol % to 99.9 mol %ethylene and/or 0.1 mol % to 99.9 mol % propylene.

In a preferred embodiment, the polymer comprises ethylene and propyleneand from 0% to 40% termonomer.

The following paragraphs enumerated consecutively from 1 through 22provide for various aspects of the present invention. In one embodiment,in a first paragraph (1), the present invention provides a transitionmetal catalyst compound represented by one of the structures:

-   1. A transition metal catalyst compound represented by the formula:

wherein

-   M is hafnium or zirconium, preferably hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may be the same or    different as R³ and preferably are both methyl; and-   each R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6    carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, provided however that at least three of    R¹⁰-R¹⁴ groups are not hydrogen (alternately four of R¹⁰-R¹⁴ groups    are not hydrogen, alternately five of R¹⁰-R¹⁴ groups are not    hydrogen).-   2. The transition metal catalyst compound of paragraph 1, wherein    each X is a methyl group.-   3. The transition metal catalyst compound of either of paragraphs 1    or 2, wherein each R¹ and R³ are methyl groups.-   4. The transition metal catalyst compound of any of paragraphs 1    through 3, wherein R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are each methyl    groups.-   5. The transition metal catalyst compound of any of paragraphs 1    through 4, wherein R², R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are all hydrogen.-   6. The transition metal catalyst compound of paragraph 1, wherein R¹    and R³ are methyl groups, R² is a hydrogen, R⁴, R⁵, R⁶, R⁷, R⁸, and    R⁹ are all hydrogens, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are all methyl    groups and each X is a methyl group.-   7. A transition metal catalyst system, comprising an activator and a    catalyst compound represented by the formula:

wherein

-   M is hafnium or zirconium, preferably hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may be the same or    different as R³ and preferably are both methyl; and-   each R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6    carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, provided however that at least three of    R¹⁰-R¹⁴ groups are not hydrogen (alternately four of R¹⁰-R¹⁴ groups    are not hydrogen, alternately five of R¹⁰-R¹⁴ groups are not    hydrogen).-   8. The catalyst system of paragraph 7, wherein each X is a methyl    group.-   9. The catalyst system of either of paragraphs 7 or 8, wherein each    R¹ and R³ are methyl groups.-   10. The catalyst system of any of paragraphs 7 through 9, wherein    R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are each methyl groups.-   11. The catalyst system of any of paragraphs 7 through 10, wherein    R², R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are all hydrogen.-   12. The catalyst system of paragraph 7, wherein R¹ and R³ are methyl    groups, R² is a hydrogen, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are all    hydrogens, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are all methyl groups and    each X is a methyl group.-   13. The catalyst system of any of paragraphs 7 through 12, wherein    the activator is selected from trimethylammonium    tetrakis(perfluorobiphenyl)borate, triethylammonium    tetrakis(perfluorobiphenyl)borate, tripropylammonium    tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium    tetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammonium    tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium    tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium    tetrakis(perfluorobiphenyl)borate,    N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(perfluorobiphenyl)borate, tropillium    tetrakis(perfluorobiphenyl)borate, triphenylcarbenium    tetrakis(perfluorobiphenyl)borate, triphenylphosphonium    tetrakis(perfluorobiphenyl)borate, triethylsilylium    tetrakis(perfluorobiphenyl)borate, benzene(diazonium)    tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B]    or mixtures thereof-   14. A process to produce vinyl terminated polymers comprising:    -   1) contacting the catalyst compound of paragraphs 1 to 6 or the        catalyst system of paragraphs 7 to 13 with olefins; and    -   2) obtaining polymer having at least 30% allyl chain ends and an        Mn of 200 g/mol or more.-   15. A process for polymerization comprising:    -   1) contacting ethylene and propylene with the compound of        paragraphs 1 to 6 or the catalyst of paragraphs 7 to 13;    -   2) obtaining polymer having an Mn of 300 to 60,000 g/mol        comprising 10 mol % to 90 mol % propylene and 10 mol % to 90 mol        % of ethylene, wherein the polymer has at least X % allyl chain        ends (relative to total unsaturations as measured by ¹H NMR),        where: 1) X=(−0.94(mol % ethylene incorporated)+100), when 10        mol % to 60 mol % ethylene is present in the polymer, and 2)        X=45, when greater than 60 mol % and less than 70 mol % ethylene        is present in the polymer, and 3) X=(1.83*(mol % ethylene        incorporated)−83), when 70 mol % to 90 mol % ethylene is present        in the polymer.-   16. The process of paragraph 14 or 15, wherein the polymer has more    than 90% allyl chain ends (relative to total unsaturations).-   17. The process of paragraph 14 or 15, wherein the polymer comprises    at 15 wt % to 95 wt % ethylene and has more than 80% allyl chain    ends (relative to total unsaturations).-   18. The process of paragraph 14 or 15, wherein the polymer comprises    at 30 wt % to 95 wt % ethylene and has more than 70% allyl chain    ends (relative to total unsaturations).-   19. The process of paragraph 14 or 15, wherein the polymer comprises    at 30 wt % to 95 wt % ethylene and has more than 90% allyl chain    ends (relative to total unsaturations).-   20. The process of paragraph 14 or 15, wherein the polymer comprises    more than 90 mol % propylene and less than 10 mol % ethylene wherein    the polymer has: at least 93% allyl chain ends, a number average    molecular weight (Mn) of about 500 to about 20,000 g/mol, an    isobutyl chain end to allylic vinyl group ratio of 0.8:1 to    1.35:1.0, and less than 1400 ppm aluminum.-   21. The process of paragraph 14 or 15, wherein the polymer comprises    at least 50 mol % propylene and from 10 mol % to 50 mol % ethylene,    wherein the polymer has: at least 90% allyl chain ends, an Mn of    about 150 to about 10,000 g/mol, and an isobutyl chain end to    allylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers    having four or more carbon atoms are present at from 0 mol % to 3    mol %.-   22. The process of paragraph 14 or 15, wherein the polymer comprises    at least 50 mol % propylene, from 0.1 mol % to 45 mol % ethylene,    and from 0.1 mol % to 5 mol % C₄ to C₁₂ olefin, wherein the polymer    has: at least 90% allyl chain ends, an Mn of about 150 to about    10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio    of 0.8:1 to 1.35:1.0.-   23. The process of paragraph 14 or 15, wherein the polymer comprises    at least 50 mol % propylene, from 0.1 mol % to 45 mol % ethylene,    and from 0.1 mol % to 5 mol % diene, wherein the polymer has: at    least 90% allyl chain ends, an Mn of about 150 to about 10,000    g/mol, and an isobutyl chain end to allylic vinyl group ratio of    0.7:1 to 1.35:1.0.-   24. The process of paragraph 14 or 15, wherein the polymer is any    polymer therein above described.

In another embodiment, this invention relates to:

-   1A. A process to produce vinyl terminated polymers comprising:    -   1) contacting:        -   a) one or more olefins with        -   b) a transition metal catalyst compound represented by the            formula:

wherein

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof;-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group; and-   each R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, provided however    that at least three of the R¹⁰-R¹⁴ groups are not hydrogen; and-   2) obtaining vinyl terminated polymer having an Mn of 300 g/mol or    more and at least 30% allyl chain ends (relative to total    unsaturation).-   2A. The process of paragraph 1A, wherein each X is a methyl group.-   3A. The process of either of paragraphs 1A or 2A, wherein each R¹    and R³ are methyl groups.-   4A. The process of any of paragraphs 1A through 3A, wherein R¹⁰-R¹⁴    are each methyl groups.-   5A. The process of any of paragraphs 1A through 4A, wherein R², R⁴,    R⁵, R⁶, R⁷, R⁸, and R⁹ are all hydrogen.-   6A. The process of paragraph 1A, wherein R¹ and R³ are methyl    groups, R² is a hydrogen, R⁴-R⁹ are all hydrogens, R¹⁰-R¹⁴ are all    methyl groups and each X is a methyl group.-   7A. The process of any of paragraphs 1A through 6A, wherein M is Hf.-   8A. The process of any of paragraphs 1A through 7A, wherein the    catalyst compound is combined with an activator.-   9A. The process of paragraph 8A, wherein the activator is    represented by the formula:

where:

-   each R₁ is, independently, a halide;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl group or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl group;-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    group, or a siloxy group of the formula —O—Si—R_(a), where R_(a) is    a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group;-   L is an neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted    acid; and d is an integer from 1 to 3;-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the B atom each have a    molecular volume of greater than 250 cubic Å.-   10A. The process of any of paragraphs 1A through 8A, wherein the    activator is selected from trimethylammonium    tetrakis(perfluorobiphenyl)borate, triethylammonium    tetrakis(perfluorobiphenyl)borate, tripropylammonium    tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium    tetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammonium    tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium    tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium    tetrakis(perfluorobiphenyl)borate,    N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(perfluorobiphenyl)borate, tropillium    tetrakis(perfluorobiphenyl)borate, triphenylcarbenium    tetrakis(perfluorobiphenyl)borate, triphenylphosphonium    tetrakis(perfluorobiphenyl)borate, triethylsilylium    tetrakis(perfluorobiphenyl)borate, benzene(diazonium)    tetrakis(perfluorobiphenyl)borate,    [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B] or mixtures thereof.-   11A. The process of any of paragraphs 1A to 10A, wherein the olefins    are ethylene and/or propylene.-   12A. The process of any of paragraphs 1A to 11A, wherein termonomer    is present at 0 mol % to 50 mol %.-   13A. The process of any of paragraphs 1A to 11A, wherein the olefin    is propylene.-   14A. The process of any of paragraphs 1A to 13A, wherein the olefins    comprises ethylene and propylene and the polyolefin obtained has a    Mn of 200 to 60,000 g/mol and comprises 0.1 to 99.9 mol % propylene    and 99.1 to 0.1 mol % of ethylene, and has at least 30% allyl chain    ends.-   15A. The process of paragraph 14A, wherein the polymer has X % allyl    chain ends (relative to total unsaturations as measured by ¹H NMR),    where: 1) X=(−0.94(mol % ethylene incorporated)+100), when 10 mol %    to 60 mol % ethylene is present in the co-polymer; and 2) X=45, when    greater than 60 mol % and less than 70 mol % ethylene is present in    the co-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83),    when 70 mol % to 90 mol % ethylene is present in the co-polymer.-   16A. The process of paragraph 14A, wherein the polymer has more than    90% allyl chain ends (relative to total unsaturations).-   17A. The process of paragraph 14A, wherein the polymer comprises at    15 wt % to 95 wt % ethylene and has more than 80% allyl chain ends    (relative to total unsaturations).-   18A. The process of paragraph 14A, wherein the polymer comprises at    30 wt % to 95 wt % ethylene and has more than 70% allyl chain ends    (relative to total unsaturations).-   19A. The process of paragraph 14A, wherein the polymer comprises at    30 wt % to 95 wt % ethylene and has more than 90% allyl chain ends    (relative to total unsaturations).-   20A. The process of paragraph 14A, wherein the polymer comprises    more than 90 mol % propylene and less than 10 mol % ethylene wherein    the polymer has: at least 93% allyl chain ends, a number average    molecular weight (Mn) of about 500 to about 20,000 g/mol, an    isobutyl chain end to allylic vinyl group ratio of 0.8:1 to    1.35:1.0, and less than 1400 ppm aluminum.-   21A. The process of paragraph 14A, wherein the polymer comprises at    least 50 mol % propylene and from 10 mol % to 50 mol % ethylene,    wherein the polymer has: at least 90% allyl chain ends, an Mn of    about 150 to about 10,000 g/mol, and an isobutyl chain end to    allylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers    having four or more carbon atoms are present at from 0 mol % to 3    mol %.-   22A. The process of paragraph 14A, wherein the polymer comprises at    least 50 mol % propylene, from 0.1 mol % to 45 mol % ethylene, and    from 0.1 mol % to 5 mol % C₄ to C₁₂ olefin, wherein the polymer has:    at least 90% allyl chain ends, an Mn of about 150 to about 10,000    g/mol, and an isobutyl chain end to allylic vinyl group ratio of    0.8:1 to 1.35:1.0.-   23A. The process of paragraph 14A, wherein the polymer comprises at    least 50 mol % propylene, from 0.1 mol % to 45 mol % ethylene, and    from 0.1 mol % to 5 mol % diene, wherein the polymer has: at least    90% allyl chain ends, an Mn of about 150 to about 10,000 g/mol, and    an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to    1.35:1.0.-   24A. The process of any of the above paragraphs 1A to 23A, wherein    the catalyst is (CpMe₂)(1,3Me₂benz[e]indenyl)HfMe₂ and the activator    is N,N-dimethylanilinium perfluorotetraphenylborate or    N,N-diMethylanilinium-tetrakis(heptafluoro-1-naphtyl)borate, where    Cp is cyclopentadienyl and Me is methyl.-   25A. The process of any of the above paragraphs 1 to 24, wherein the    polymer has an Mn of from 300 to 60,000 g/mol.-   26A. A transition metal catalyst composition represented by the    formula:

wherein

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof;-   each R¹ and R³ are, independently, a C₁ to C₈ alkyl group; and-   R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,    independently, hydrogen, or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, provided,    however, that at least three of the R¹⁰-R¹⁴ groups are not hydrogen;    and an activator.-   27A. The transition metal catalyst composition of paragraph 26A,    wherein each X is a methyl group.-   28A. The transition metal catalyst composition of either of    paragraphs 26A or 27A, wherein each R¹ and R³ are methyl groups.-   29A. The transition metal catalyst composition of any of paragraphs    26A through 28A, wherein R¹⁰-R¹⁴ are each methyl groups.-   30A. The transition metal catalyst composition of any of paragraphs    26A through 29A, wherein R², R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are all    hydrogen.-   31A. The transition metal catalyst composition of paragraph 26A,    wherein R¹ and R³ are methyl groups, R² is a hydrogen, R⁴-R⁹ are all    hydrogens, R¹⁰-R¹⁴ are all methyl groups and each X is a methyl    group.-   32A. The transition metal catalyst composition of any of paragraphs    26A through 31A where M is Zr.-   33A. A polymer of propylene produced by any of process paragraphs 1A    to 25A.-   34A. A polymer of propylene having an Mn of more than 30,000 g/mol    and at least 30% allyl chain ends (relative to total unsaturation).-   35A. The polymer of paragraph 34A, where the polymer has an isobutyl    chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,    optionally less than 1400 ppm aluminum.

EXAMPLES Metallocene Syntheses

Typical dry-box procedures for synthesis of air-sensitive compounds werefollowed including using dried glassware (90° C., 4 hours) and anhydroussolvents purchased from Sigma Aldrich (St. Louis, Mo.) which werefurther dried over 3 A sieves. 3H-Benz[e]indene (Benzo(4,5)indene) waspurchased from Boulder Scientific (Boulder, Colo.).Pentamethylcyclopentadiene was purchased from Norquay. All otherreagents were purchased from Sigma-Aldrich.

Synthesis of [Li][1,3-Dimethylbenz[e]indene]

[Li][Benz[e]indene] was generated in ether by the reaction of3H-Benz[e]indene (12.0 g, 0.072 mol) with 1.1 equivalents of n-BuLi(7.90 mL of 10 M/hexane, 0.079 mol) which was added slowly. After 2hours, the [Li][Benz[e]indene] was isolated by removal of the etherunder vacuum. The residue was triturated with hexane to give anoff-white solid. The solid was collected on a medium sized glass frit byvacuum filtration, washed with excess hexane and dried in vacuo,providing pure [Li][Benz[e]indene] as an off-white solid (12.0 g, 97%).The product was characterized by ¹H NMR: (THF-d_(g), 250 MHz) δ ppm:8.02 (d, J=10 Hz, C₁₀H₆, 1H), 7.47 (t, J=6.3 Hz, C₁₀H₆, 2H), 7.09 (t,J=6.2 Hz, C₁₀H₆, 1H), 6.91 (t, J=1 Hz, C₁₀H₆, 1H), 6.74 (d, J=10 Hz,C₁₀H₆, 1H), 6.59 (s, indenyl proton, 1H), 6.46 (s, indenyl proton, 1H),6.46 (s, indenyl proton, 1H), 6.09 (s, indenyl proton, 1H).

[Li][Benz[e]indene] (12.0 g, 0.070 mol) was dissolved in ether, cooledto −35° C. and reacted with 6.0 equivalents of MeI (59.34 g, 0.418mmol). The reaction was allowed to warm to ambient temperature. After 12hours, the reaction was quenched with water and extracted with ether.The organics were concentrated to yield a crude oil which was distilledusing Kugelrohr apparatus to provide a clear oil which was a cleanmixture of 3-methyl-3H-benz[e]indene and 1-methyl-1H-benz[e]indeneisomers (7.58 g, 58%). The product was characterized by ¹H NMR: (CD₂Cl₂,250 MHz) δ ppm: 8.25-7.42 (m, C₁₀H₆, 10H), 7.15 (d, J=6.3 Hz, C₁₀H₆,2H), 7.09 (t, J=6.2 Hz, C₁₀H₆, 1H), 6.91 (t, J=1 Hz, C₁₀H₆, 1H), 6.74(d, J=10 Hz, C₁₀H₆, 1H), 6.59 (s, indenyl proton, 1H), 6.46 (s, indenylproton, 1H), 6.46 (s, indenyl proton, 1H), 6.09 (s, indenyl proton, 1H).

Similarly, [Li][methylbenz[e]indene] was generated in ether by thereaction of the isomer mix of 3-methyl-3H-benz[e]indene and1-methyl-1H-benz[e]indene (7.58 g, 0.041 mol) with 1.1 equivalents ofn-BuLi (4.45 mL of 10 M/hexane, 0.045 mol) which was added slowly. After2 hours, the [Li][methylbenz[e]indene] was isolated by removal of theether under vacuum. The residue was triturated with hexane to give anoff-white solid. The solid was collected on a medium sized glass frit byvacuum filtration, washed with excess hexane and dried in vacuo,providing pure [Li][methylbenz[e]indene] as an off-white solid (6.97 g,85%).

[Li][methylbenz[e]indene] (6.97 g, 0.037 mol) was dissolved in ether,cooled to −35° C. and reacted with 3.7 equivalents of MeI (19.52 g,0.138 mmol). The reaction was allowed to warm to ambient temperature.After 12 hours, the reaction was quenched with water and extracted withether. The organics were concentrated to yield a yellow oil which was amixture of 1,3-dimethyl-3H-benz[e] indene, 1,3-dimethyl-1H-benz[e]indene, 3,3-dimethyl-3H-benz[e]indene, and 1,1-dimethyl-1H-benz[e]indeneisomers (6.63 g, 91%).

Similarly, [Li][1,3-Dimethylbenz[e]indene] was generated in ether by thereaction of the dimethylbenzindene isomer mixture above (6.63 g, 0.034mol) with 1.1 equivalents of n-BuLi (3.74 mL of 10 M/hexane, 0.037 mol)which was added slowly. After 2 hours, the[Li][1,3-Dimethylbenz[e]indene] was isolated by removal of the etherunder vacuum. The residue was triturated with hexane to give anoff-white solid. The solid was collected on a medium sized glass frit byvacuum filtration, washed with excess hexane and dried in vacuo,providing pure [Li][1,3-Dimethylbenz[e]indene] as an off-white solid(5.43 g, 79%). The product was characterized by ¹H NMR: (THF-d₈, 250MHz) δ ppm: 8.19 (d, J=7.5 Hz, 1H), 7.48 (d, J=7.5 Hz, 1H), 7.33 (d,J=7.5 Hz, 2H), 7.09 (t, J=1.4 Hz, 1H), 6.91 (t, J=1.2 Hz, 1H), 6.67 (d,J=8.5 Hz, 1H), 5.98 (s, 1H), 2.65 (s, 3H), 2.34 (s, 3H).

Synthesis of (CpMe₅)(1,3-Me₂-benz[e]indenyl)HfMe₂ (2)

CpMe₅HfCl₃ (3.8 g) was reacted with [Li][1,3-Me₂-benz[e]indenyl] (2.5 g,4.3 mmol) in Et₂O (80 ml) for 48 hrs. (Crowther, D.: Baenziger, N.;Jordan, R.; J. Journal of the American Chemical Society (1991), 113(4),pp. 1455-1457.) The pale yellow product was collected by filtration overa glass frit and dried to yield crude(CpMe₅)(1,3-Me₂-benz[e]indenyl)HfCl₂ (3.2 g) as a mixture with LiCl. ¹HNMR (CD₂Cl₂, 250 MHz) δ ppm; 8.13, 7.80 (d, Ha, Ha′, 1H), 7.59 to 7.36(multiplets, Hb, Hb′, Hc, Hc′, 4H) 6.10 (s, Hd, 1H), 2.62, 2.45 (s,1,3Me₂C₉H₅, 3 H), 2.10 (s, CpMe₅).

(CpMe₅)(1,3-Me₂-benz[e]indenyl)HfCl₂ (2.5 g) was slurried in toluene(100 ml) and reacted with MeMgI (4.2 g, 2.1 equiv, 3.0 M in Et₂O). Thereaction mixture was heated to 80° C. for 3 hrs. After cooling thevolatiles were removed in vacuo to yield a solid which was extractedwith hexane (4×40 ml). Hexane was removed from the combined extractionsto yield solid yellow (CpMe₅)(1,3-Me₂C₉H₅)HfMe₂ (1.6 g). ¹H NMR(C₆D₆,300 MHz) δ ppm; 7.55-7.48 (m, C₆H₄, 2H), 7.20-7.16 (m, C₉H₅, 3H), 2.00(s, 1,3Me₂C₉H₅, 6H), 1.76 (s, CpMe₅, 15H), −0.95 (s, Hf-Me, 6H).

Polymerizations

Batch polymerizations were carried out using a 2 L stirred autoclavereactor. Polymerization conditions used with 2(CpMe₅)(1,3Me₂-benz[e]indenyl)HfMe₂ are described in Table 1. Catalystsolutions were prepared in a dry nitrogen purged Vacuum Atmospheres™ drybox by adding nearly equimolar (typically 1.00:1.05) quantities ofmetallocene and activator to 2 mL dry toluene in a 10 mL glass vial. Themixture was stirred for several minutes and then transferred to a clean,oven dried catalyst tube. An example of the basic polymerizationprocedure follows: 2 mL at 25 wt % tri-n-octyl aluminum(TNOA)-in-hexanes scavenger and 500 mL propylene were added to reactor,the reactor was heated to 70° C., then catalyst 2/activator A(N,N-dimethylaniliniumperfluorotetraphenylborate) were flushed from thecatalyst tube into the reactor with 500 mL hexanes. Polymerization wascarried out for 30 minutes, then the reactor was cooled, depressurized,and opened. The residual propylene and hexanes concentration in theproduct was reduced either through “weathering” or by heating the samplein the oven under nitrogen purge. Some of the lowest molecular weightoligomer product was presumed lost along with the propylene. In somecases, residual propylene was still detected in the product in ¹H NMRsrecorded at 30° C. (not detected when spectra recorded at 120° C.).

TABLE 1 Summary of Polymerizations with catalyst 2/Activator A withpropylene Cat/Activator Tp. Time Yield Run Hexanes, Vol % (mg/mg) (C)(min) (g) 1 0 5/11.3 44 70 480 2 50 5/11.3 40 70 228 3 75 5/11.3 40 7092 4 0 5/11.3 70 30 215 5 50 5/11.3 70 30 102 6 75 5/11.3 70 60 68

The impact of propylene concentration on catalyst productivity recordedat two different temperatures is shown in FIG. 1.

Product Characterization

Products prepared with 2 were characterized by ¹H NMR and GPC-DRI (PPstd). ¹H NMR spectra were recorded for solutions of polymer dissolved inCDCl₃ (30° C.) or tetrachloroethane-d₂ (120° C.) (TMS lock). ¹H NMR dataare summarized in Table 2. Products made with 2 and Activator A retainhigh allylic vinyl populations—96% to 97%).

GPC-DRI data are reported in Table 3.

TABLE 2 ¹H NMR Results for Allylic Vinyl Polypropylene Unsats/1000 C.Vinylenes + % MN Run olefins vinyls vinylidenes Vinyl DP ¹H NMR 1 0.209.62 0.07 97.27 33.70 1415.6 2 0.33 15.46 0.2 96.5 20.8 874 3 2.31 23.480 90.8 12.9 541 4 0.8 39.45 0.5 96.9 8.19 343.8 5 0.8 42.5 0.6 96.8 7.6319.1 6 1.1 45.5 0.8 96.0 7.0 295.2 DP = Degree of Polymerization

TABLE 3 GPC-DRI Results (iPP Standard) Run MN ¹H NMR Mn Mw Mz Mn/Mw* 11415.6 884 3,574 8,430 4.04 2 874 511 1561 8872 3.05 3 541 363 794 17682.18 4 343.8 131 493 3827 3.76 5 319.1 185 279 460 1.51 6 295.2 167 244386 1.46 *Both determined by GPC

Continuous polymerization of propylene-ethylene polymer was conducted ina 1 liter internal volume Continuous Flow Stirred Tank Reactor usingisohexane as the solvent. The liquid full reactor had a variableresidence time of approximately 15 to 45 minutes and the pressure wasmaintained at 320 psig (2206 kPa). A mixed feed of isohexane, ethyleneand propylene was pre-chilled to approximately −30° C. to remove theheat of polymerization, before entering the reactor. The pre-chillingtemperature was adjusted to maintain indicated solution polymerizationtemperature. The solution of catalyst/activator in toluene and thescavenger in isohexane were separately and continuously admitted intothe reactor to initiate the polymerization. The reactor temperature wasvaried from between 50° C. and 60° C.

Isohexane, ethylene, and propylene were fed to the reactor at the ratesshown in Table 4. The catalyst 2 was activated in vitro with 1:102 molarratio with N,N′-Dimethyl anilinium-tetrakis(heptafluoro-1-naphthyl)borate indicated below in Table 4 and introducedinto the polymerization reactor at the rates indicated in Table 4. Adilute solution of tri n-octyl aluminum was introduced into the reactoras a scavenger. A rate of approximately 5.16 X 10-3 mmol/min ofscavenger was fed continuously into the unit for this polymerization.After five residence times of steady polymerization, a representativesample of the polymer produced in this polymerization was collected. Thesolution of the polymer was withdrawn from the top, and then steamdistilled to isolate the polymer. The polymerization product wascollected for a certain time and conversions calculated as shown inTable 7. The polymer produced in this polymerization was analyzed forethylene content by FT-IR (reported in Table 6) and by GPC (reported inTable 6). Unsaturated chain ends were determined by ¹H NMR (6+120° C.)and are reported in Table 7.

TABLE 4 C3 Feed C2 Feed Isohexane Catalyst Activator Scavenger Rate,Rate, Feed Rate, Feed Rate, Feed Rate, Feed Rate, Run Temp, ° C. g/ming/min g/min mol/min mol/min mol/min A 60 5 1 59.5 1.24 × 10⁻⁷ 1.27 ×10⁻⁷ 5.16 × 10⁻⁶ B 60 10 2 59.5 2.48 × 10⁻⁷ 2.53 × 10⁻⁷ 5.16 × 10⁻⁶ C 5015 3 59.5 2.48 × 10⁻⁷ 2.53 × 10⁻⁷ 5.16 × 10⁻⁶ D 50 15 5 59.5 1.86 × 10⁻⁷1.90 × 10⁻⁷ 5.16 × 10⁻⁶

TABLE 5 H NMR - (Unsat/1000 C.) % % vi- Run vinylenes olefins vinylsvinylidenes vinyls nylidenes A 0.04 0.38 15.5 0.27 96 1.7 B 0.02 0.3916.1 0.28 96 1.7 C 0.02 0.26 11 0.16 96 1.4 D 0.01 0.12 6.14 0.1 96 1.6

TABLE 6 wt % Mn by GPC-DRI C2, Run ¹H NMR Mn Mw Mz Mw/Mn FTIR A 2150 4811182 2392 2.457 51 B 1877 446 1184 2439 2.655 45 C 1638 710 1960 39702.761 39 D 2268 1416 5127 46771 3.621 54

TABLE 7 Con- collec- ver- tion Temp, sion, time, met mol × yield yield,Run C. yield, g % min 10 − 7/min Kg/mol Kg/g A 60 267.8 23.5 190 1.2411367 21 B 60 484.3 20.2 200 2.48 9764 18 C 50 1240.7 38.3 180 2.4827793 52 D 50 1052.1 39 135 1.86 41900 78

Example A Comparison of Activators I to III

Polymerizations were conducted in an inert atmosphere (N₂) drybox using48 Cell Parallel Pressure Reactors (PPR) equipped with external heatersfor temperature control, glass inserts (internal volume of reactor=22.5mL), septum inlets, regulated supply of nitrogen, propylene, andequipped with disposable PEEK (PolyEtherEtherKetone) mechanical stirrers(800 RPM). The PPRs were prepared for polymerization by purging with drynitrogen at 150° C. for 5 hours and then at 25° C. for 5 hours. Thereactors were heated to 25° C. and propylene was then charged to thereactor. A solution of scavenger/co-catalyst at process temperature andpressure was next added to the reactors via syringe. The reactors wereheated to process temperature (85° C.) and stirred at 800 RPM. Catalystwas mixed with the activator and stirred in toluene at ambienttemperature and pressure and added to the reactors (at processtemperature and pressure) via syringe as a solution to initiatepolymerization. Because the solutions are added via syringe, a hexanessolution is also injected via the same syringe following their additionto insure that minimal solution is remaining in the syringe. Thisprocedure is applied after the addition of the scavenger/co-catalystsolution as well as the catalyst solution. Propylene was allowed toenter the reactors to a desired pressure through the use of regulatorsand allowed to drop during the polymerization. No pressure control wasemployed during the run. Reactor temperatures were monitored andtypically maintained within a +/−1° C. temperature range.Polymerizations were quenched by the addition of approximately 50 psi(345 kPa) delta of Industrial Grade Air for approximately 60 seconds.The polymerizations were quenched after the desired polymerization time.The reactors were cooled and vented. The polymer was isolated after theremaining reaction components were removed in-vacuo. Yields reportedinclude total weight of polymer and residual catalyst. Yields are listedin Table A, below. Run time was varied, as indicated in Table A;Activator to metallocene ratio was 1:1; Reaction temperature was 85° C.;catalyst concentration was 5×10⁻⁵ mol/L; TNOAL concentration was1.2×10⁻⁴ mol/L. Total solution volume was 5 mLs.

TABLE A Comparison of Activators I to III Metallocene Run (MCN)Activator [C3], mol/L Run Time, s Yield, mg A1 E I 1.4 300.7 62.7 A2 E I1.4 216.1 87.5 A3 E III 1.4 298.3 80 A4 E III 1.4 301.3 82.1 A5 E II 1.4303 79.6 A6 E II 1.4 286.8 78 B1 G I 1.4 211.7 103.5 B2 G I 1.4 219.5107.3 B3 G III 1.4 217.8 99.1 B4 G III 1.4 213.9 107.4 B5 G II 1.4 243.6104.9 B6 G II 1.4 300.7 92.9 C1 A I 1.4 71.3 163.4 C2 A I 1.4 71.6 170C3 A III 1.4 94.5 157.3 C4 A III 1.4 80.8 145.5 C5 A II 1.4 99.1 148.5C6 A II 1.4 103.7 154.9 D1 G I 1.4 61.1 190.9 D2 G I 1.4 60.2 197.9 D3 GIII 1.4 76.2 166.1 D4 G III 1.4 74.8 178.9 D5 G II 1.4 117.7 155 D6 G II1.4 115.9 156 E1 E I 2.9 198 125.4 E2 E I 2.9 141.5 144.7 E3 E III 2.9144.7 137.3 E4 E III 2.9 171 133.4 E5 E II 2.9 189.1 135.5 E6 E II 2.9175.2 121.5 F1 G I 2.9 138.7 147.6 F2 G I 2.9 173.2 141.9 F3 G III 2.9161.3 150.4 F4 G III 2.9 125.2 165.4 F5 G II 2.9 127.9 163 F6 G II 2.9157.4 139.4 G1 A I 2.9 55.4 265.5 G2 A I 2.9 56.1 271.5 G3 A III 2.975.7 245.2 G4 A III 2.9 90.5 234 G5 A II 2.9 80.5 233.4 G6 A II 2.9 81.8240.7 H1 G I 2.9 37 296.7 H2 G I 2.9 45.4 326.9 H3 G III 2.9 54.2 319.3H4 G III 2.9 49 294.6 H5 G II 2.9 72.2 281.3 H6 G II 2.9 78.6 276.5

Data from the analysis of some of the cell products is shown in theTable 5B, below.

TABLE 5B Data for Comparison of Activators I to III % Yield Vi- % Mn MnMw/Mn Run MCN ACT g nyls VYD (HNMR) (GPC) (GPC) A1 E I 0.063 88 12 655 —— A2 E I — — — — 1137 2.2 A3 E III 0.08 98.6 1.4 642 1072 2.9 A5 E II0.08 99.2 0.8 786 857 1.6 B1 G I 0.104 52.2 47.8 683 745 1.4 B3 G III0.099 92.4 7.6 1018 4416 2.3 B5 G II 0.105 95.7 4.3 1073 1079 1.7 C1 A I0.163 70.8 29.2 4806 2775 3.1 C3 A III 0.157 91.2 6.3 7441 5754 2.2 C5 AII 0.149 85.5 12.8 7119 6326 2.1 D1 G I 0.191 31.8 62.5 16,712 13,5972.6 D3 G III 0.166 66.1 33.8 32,186 36,789 2.4 D5 G II 0.155 57.4 41.338,166 34,217 2.3 G1 A I 0.266 71.5 27.2 4424 — — G3 A III 0.245 91.35.9 7762 — — G5 A II 0.233 81.6 13.5 9277 — — KEY: MCN = metallocene,ACT = activator, VYD = vinylideneMetallocenes Used in Example A

The following metallocenes were used in Example A.

Metallocene Structure A

B

C

D

E

F

G

Activators Used

The following activators were used in Example A.

Activator Chemical Name IDimethylaniliniumtetrakis(pentafluorophenyl)borate IIDimethylaniliniumtetrakis(perfluorobiphenyl)borate IIIDimethylaniliniumtetrakis(perfluoronaphthyl)borate

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications, and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is NOT incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A propylene-ethylene copolymer having an Mn ofmore than 30,000 g/mol and up to 60,000 g/mol, and at least 90% allylchain ends relative to total unsaturation; and wherein the polymer isproduced with a single metallocene catalyst at a temperature within therange of 25 to 150° C. and a pressure within the range of 0.45 to 6 MPa.2. The copolymer of claim 1, where the polymer has an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.3:1.0, and has less than 1400ppm aluminum.
 3. The copolymer of claim 1, wherein the polymer has atleast 95% allyl chain ends relative to total unsaturation.
 4. Thecopolymer of claim 1, wherein the polymer has an Mn of more than 30,000g/mol up to 40,000 g/mol.
 5. The copolymer of claim 1, wherein thepolymer has an Mn of more than 30,000 g/mol up to 60,000 g/mol andcomprises 90 to 40 mol% propylene and 10 to 60 mol% of ethylene, whereinthe copolymer has at least X% allyl chain ends relative to totalunsaturation, where: X=(−0.94(mol% ethylene incorporated)+100).
 6. Thecopolymer of claim 1, wherein the polymer has an Mn of more than 30,000g/mol up to 60,000 g/mol and comprises 10 to 30 mol% propylene and 70 to90 mol% of ethylene.
 7. The copolymer of claim 1, wherein the polymerhas a melting point of 100° C. or more.
 8. The copolymer of claim 1,wherein the polymer has a Tg of 0° C. or less.
 9. The copolymer of claim1, wherein the polymer has a melting point of 150° C. or more.
 10. Thecopolymer of claim 1, wherein the polymer has less than 1400 ppm ofaluminum.
 11. The copolymer of claim 1, wherein the polymer has lessthan 25 ppm of hafnium.
 12. The copolymer of claim 1, wherein thepolymer has a melting point of from 60 to 130° C.
 13. The copolymer ofclaim 1, wherein the polymer has a Tg of −10° C. or less.
 14. Thecopolymer of claim 1, wherein the polymer has a Tg of −20° C. or less.15. The copolymer of claim 1, wherein the polymer has a Tg of −30° C. orless.
 16. The copolymer of claim 1, wherein the polymer has a Tg of −50°C. or less.
 17. A propylene-ethylene copolymer having an Mn of from 300to 30,000 g/mol and at least 90% allyl chain ends relative to totalunsaturation; and wherein the polymer is produced with a singlemetallocene catalyst at a temperature within the range of 25 to 150° C.and a pressure within the range of 0.45 to 6 MPa.
 18. The copolymer ofclaim 17, where the polymer has an isobutyl chain end to allylic vinylgroup ratio of 0.8:1 to 1.3:1.0, and has less than 1400 ppm aluminum.19. The copolymer of claim 17, wherein the polymer has an Mn of morethan 30,000 g/mol up to 100,000 g/mol.
 20. The copolymer of claim 17,wherein the polymer has an Mn of more than 30,000 g/mol up to 40,000g/mol.
 21. The copolymer of claim 17, wherein the polymer has an Mn ofmore than 30,000 g/mol up to 60,000 g/mol and comprises 90 to 40 mol%propylene and 10 to 60 mol% of ethylene, wherein the copolymer has atleast X% allyl chain ends relative to total unsaturation, where:X=(−0.94(mol% ethylene incorporated)+100).
 22. The copolymer of claim17, wherein the polymer has a melting point of 100° C. or more.
 23. Thecopolymer of claim 17, wherein the polymer has a Tg of 0° C. or less.24. The copolymer of claim 17, wherein the polymer has a melting pointof from 60 to 130° C.
 25. The copolymer of claim 17, wherein the polymerhas a Tg of−10° C. or less.